Phenanthroline antifoggants for silver halide emulsions

ABSTRACT

A photographic material comprising phenanthroline antifogging agents for silver halide emulsions.

United States Patent Inventors Appl. No.

Priority Toshihiko Yamamoto Tokyo;

Kazuo Matui, Tokyo; Sadao Sugita, Hanno, all of Japan Mar. 30, 1970 Oct. 26, 1971 Konishiroku Photo Industry Co., Ltd. Tokyo, Japan Mar. 25, 1969 Japan PHENANTHROLINE ANTIFOGGANTS FOR SILVER HALIDE EMULSIONS 4 Claims, No Drawings US. Cl 96/109, 96/ I 00 [51] Int. Cl.

G03c 1/34 [50] Field of Search 96/109, 100, 66.5 56] References Cited UNITED STATES PATENTS 3,220,935 I 1/1965 Nations et al 203/6 FOREIGN PATENTS 587,481 4/1947 Great Britain 96/106 Primary Examiner-Norman G. Torchin Assistant Examiner-Won H. Louie, Jr. Attorney-Waters, Roditi, Schwartz & Nissen ABSTRACT: A photographic material comprising phenanthroline antifogging agents for silver halide emulsions.

PHENANTHROLINE ANTIFOGGANTS FOR SILVER HALIDE EMULSIONS This invention relates to a light-sensitive silver halide photographic material characterized in that a certain phenanthroline has been incorporated as an antifoggant into at least one of the layers constituting the photographic material.

Generally, a light-sensitive silver halide photographic material tends to form fog when treated with a developer at a relatively high temperature. It is well known that such fog formation is ascribable to the fact that the activation energy of development of fog is greater than that of development of image at a high temperature. Accordingly, the development of photographic material at elevated temperatures should be avoided as far as possible. In practice, however, there are many cases where the adoption of a relatively high temperature is inevitable owing to weather conditions or the adoption of a particularly high developer temperature is necessary in carrying out rapid development. For these reasons, there has been desired the production of light-sensitive photographic materials which are less in fog and stain even when developed at elevated temperatures. Hitherto, however, no light-sensitive photographic material satisfying the said desire has yet been obtained.

With an aim to satisfy the above-mentioned desire, the present inventors made extensive studies to find that when a phenanthroline represented by the formula wherein X is a hydrogen or halogen atom, or an alkyl or aryl group or a group derived therefrom; Z is a hydrogen atom, or an alkyl or aryl group or a group derived therefrom; and Y is a hydrogen atom, or an alkyl or alkoxy group or a group derived therefrom, is incorporated into at least one of the emulsion layer, sublayer, interlayer, protective layer and backing layer constituting a light-sensitive silver halide photographic material, the photographic material is not only greatly decreased in formation of fog and in formation of color fog and stain in color photography which are brought-about due to high-temperature development, but also is enhanced in storability.

Typical examples of the compounds represented by the above-mentioned formula which are used in the present invention are as shown in the table below, but it is needless to say that compounds usable in the present invention are not limited These compounds may be effectively incorporated into any layers constituting light-sensitive materials, but are most preferably incorporated into photographic emulsions which have completed second ripening. Alternatively, however, they may also be incorporated into photographic emulsions before or during second ripening thereby to prevent the formation of fogged nucleus. Further, the compounds may be applied to socalled protect-type color photographic emulsions by mixing them with water-insoluble or difficultly water-soluble couplers, dissolving the mixtures in water-immiscible highboiling solvents and then dispersing the solutions in the photographic emulsions.

The amounts of the compounds to be incorporated vary depending on the kind of the emulsions, the kind of the compounds, the conditions of desired fog inhibition, etc. Generally, however, they are used in amounts of 10 mg. to 1.0 g. per liter of the silver halide emulsions and are incorporated in the form of solutions in a suitable organic solvent such as, for example, methanol, ethanol, acetone, ethyl acetate or the like.

In case the compound is desired to be incorporated into auxiliary layers other than the emulsion layer, the amount of the compound is so controlled, in principle, that after prepara tion of light-sensitive material, the total amount of the compound per unit area becomes an amount within the abovementioned range.

In embodying the present invention, the photographic emulsions may have been subjected to gold sensitization, sulfur sensitization and the like chemical sensitization or to spectral sensitization and the like. The compounds employed in the present invention can inhibit the formation of fog, which is liable to be formed due to said sensitization.

The present invention is illustrated in further detail below with reference to examples.

EXAMPLE 1 A high-speed silver iodobromide emulsion for X-ray films was subjected to ordinary chemical ripening. To this emulsion were added mg. per cc. of the emulsion of 5-methyl-7- hydroxy-S-triazolo (2,3-a) pyrimidine as a stabilizer and 1 g. of saponin as a coating aid. The thus-treated emulsion was divided into 9 portions, and the 8 portions were individually incorporated with each of the compounds set forth in the table below, while the remaining 1 portion was left unincorporated. These emulsions were individually coated on a triacetate film base, followed by drying to prepare photographic films. Each of the thus prepared films was exposed according to the only to these compounds. 50 procedure described in HS K7609, was developed at 30C C.

Compound (I) (II) (III) (IV) (VII) (VIII) X H N02 01 OH; H H

H H H H H Q Q Y H H H H H H CH; H

(X) (XI) (XII) (XIII) (XIV) (XV) X H -CHa tC4Ho H QC] "C3111 Z H H H CH3 Q-som --cm c1 Y CH; H CH; OOHa -0CzH4 CH; OCHa The phenanthroline compounds represented by the abovementioned formula are available in market as metal-chelating agents and colorimetric reagents.

for 1 minute and 30 seconds, at 35C. for 40 seconds and at 40C. for 25 seconds with a strongly alkaline PQ developer containing l-phenyl-3-pyrazolidone-hydroquinone and was then subjected to measurements of speed and fog to obtain the results shown in the following table:

pounds set forth in the table below, while the remaining one portion was left unincorporated. These emulsions were in- Amount incorporated 30 C., 1.5 min. 35 C., 40 sec. 40 C., 25 sec.

per liter of emulsion Relative Relative Relative Compound incorporated (mg.) speed og speed Fog speed Fog None 100 0. 20 100 0.42 100 0. 76 Exemplified compound (II 180 100 0. 08 100 0.12 100 0. 18 Exemplified compound (IV 230 95 O. 07 95 0. 12 93 0. 17 Exemplified compound (V) 260 100 0. 06 100 0. 10 95 0. 13 Exemplified compound (V 220 100 0.03 100 0. 100 0. Exemplified compound (VII) 250 95 0. 05 95 0.06 90 0. 08 Exemplified compound (IX) 310 100 0. 12 90 0. 18 90 0. 23 Exemplified compound (X) 350 100 0.07 90 0.10 87 0. 16 Exemplified compound (XII) 280 100 0. 09 100 0. 12 100 0. 21

2O dividually coated on a photographic raw paper, followed by As is clear from the above table, the photographic materials incorporated with the compounds used in the present invention are inhibited in formation of fog owing to development without any detrimental effect on speed.

EXAMPLE 2 To a green-sensitive high-speed silver iodobromide color photographic emulsion were added mg. per I00 cc. of the emulsion of 5-methyl-7-hydroxy-S-triazolo (2,3-a) pyrimidine as a stabilizer and a solution in IN-caustic soda of 15 g. of a magenta coupler l-(4-carboxyphenyl)-3-(4-palmitoylaminobenzoylamino)S-pyrazolone, and the thus treated emulsion was adjusted to pH 6.8 by addition of citric acid. This emulsion was divided in the same manner as in example 1, and the divided emulsions were individually incorporated with each of the compounds set forth in the table below and then coated on a film base, followed by drying to prepare color photographic films. Each of the thus prepared films was developed at 23C. for 9 minutes and at 25C. for 6 minutes with a color drying to prepare color photographic printing papers. Each of the thus prepared printing papers was developed at 28C. for 4 minutes with a color developer containing p-aminoethylhydroxyethylaniline, was subjected to fixing, water-washing, bleaching, fixing, water-washing and drying in this order and was then measured in speed and fog to obtain the results shown in the following table:

Amount developer containing diethyl-p-phenylenediamine, and then subjected to water-washing, bleaching, water-washing, fixing, As is apparent also from the above table, the light-sensitive water-washing and drying in this order. Thereafter the meamaterials incorporated with the compounds employed in the surements of speed and fog were effected to obtain the results 'present invention inhibit the color fog formed at the time of as shown in the following table: color development without any detrimental effects on speed.

Amount incor- 23 C., 9 min. 25 C., 6 min.

porated per liter of emul- Relative Developed Relative Developed Compound incorporated sion (mg.) speed fog density speed fog density None 100 0.10 100 0. 16 Exemplified compound (I) 120 105 0.02 100 0.05 Exemplified compound (II) 120 100 0.02 95 0.07 Exemplified compound (VI)- 120 95 0. 03 90 0.06 Exemplified comp and (VIII) 120 100 0.02 100 0.04 Exemplified compound (IX) 120 100 0. 03 95 0. (Y7 Exemplified compound (XI)--- 120 100 0. 03 90 0. 05 Exemplified compound (XIV) 120 90 0.02 95 0.05

As is clear from the above table, the light-sensitive photographic materials in accordance with the present invention successfully inhibit the color fog formed at the time of color development.

EXAMPLE 4 EXAMPLE 3 Each of the exemplified compounds (I), (IV), (Vlll) and To a red-sensitive low-speed silver chlorobromide color (XIV) was formed into a 2 percent methanol solution and was photographic emulsion containing 25 mole percent of silver incorporated in such amount as shown in the table below into bromide were added 100 mg. per liter of the emulsion of 5- I a 3 percent aqueous gelatine solution. To this solution was methyl-7-hydroxy-S-triazolo (2,3-a) pyrimidine as a stabilizer further added 20 cc. of a 5 percent saponin solution as a coatand a solution in lN-caustic soda of 20 g. of a cyan coupler loxy-4-sulfo-2-naphthoic octadecylamide, and the thus treated emulsion was adjusted to pH 6.5 by addition of citric acid. The emulsion was divided into eight portions, and the seven portions were individually incorporated with each of the coming aid, and the resulting mixed solution was applied as a protec tive layer to a high-speed X-ray film and was then dried. The thus obtained photographic films and a photographic film prepared without use of any such compound as mentioned above were subjected to high-temperature development in the wherein X is a hydrogen or halogen atom, or an alkyl or aryl group or a group derived therefrom; Z is a hydrogen atom, or

entirely same manner as in example 1 and were then measured in speed and fog to obtain the results as set forth in the following table: an alkyl or aryl group or a group derived therefrom; and Yrs a Amount iucor- 30 0., 1.5 min. 35 0., 40 sec. 40 0., 25 sec.

porated per liter of 3% Relative Relative Relative Compound incorporated gelatine (mg.) speed Fog speed Fog speed Fog None 100 0.18 100 0. 28 100 0. 56 Exemplified compound (I)... 200 105 0.06 100 0.10 105 0.18 Exemplified compound (IV) 240 95 0.08 100 0.12 100 0.22 Exemplified compound (VIII)- 250 110 0.08 105 0. 18 110 0.27 Exemplified compound (XIV)- 200 95 0. 05 100 0. 07 110 0. 10

hydrogen atom, or an alkyl or alkoxy group or a group derived therefrom.

2. A light-sensitive silver halide photographic material as claimed in claim 1, wherein said phenanthroline is in at least one layer selected from the emulsion layer, sublayer, interlayer, protective layer and backing layer.

3. A light-sensitive silver halide photographic material as claimed in claim 1, wherein said phenanthroline is incorporated together with a color coupler into one or more emulsion layer to constitute a light-sensitive silver halide colorphotographic material.

4. A light-sensitive silver halide photographic material as claimed in claim 1, wherein the amount of said phenanthroline contained is 10 mg. to 1.0 g. per liter of the silver halide emulsion used. 

2. A light-sensitive silver halide photographic material as claimed in claim 1, wherein said phenanthroline is in at least one layer selected from the emulsion layer, sublayer, interlayer, protective layer and backing layer.
 3. A light-sensitive silver halide photographic material as claimed in claim 1, wherein said phenanthroline is incorporated together with a color coupler into one or more emulsion layer to constitute a light-sensitive silver halide color-photographic material.
 4. A light-sensitive silver halide photographic material as claimed in claim 1, wherein the amount of said phenanthroline contained is 10 mg. to 1.0 g. per liter of the silver halide emulsion used. 